CN1513891A - Biodegradable water absorprion agent and its microorganism composite preparation method - Google Patents

Biodegradable water absorprion agent and its microorganism composite preparation method Download PDF

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Publication number
CN1513891A
CN1513891A CNA031109829A CN03110982A CN1513891A CN 1513891 A CN1513891 A CN 1513891A CN A031109829 A CNA031109829 A CN A031109829A CN 03110982 A CN03110982 A CN 03110982A CN 1513891 A CN1513891 A CN 1513891A
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water
agent
microorganism
bacterium mud
biodegradable
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CNA031109829A
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田玉忠
刘宝臣
遆铁军
刘贵峰
张苏德
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Abstract

A biodegradable hydroscopic agent for agricultural crops is prepared from starch, acrylic acid, ammonia water, potassium persulfate as catalyst, propanetriol as cross-linking agent and wet bacterial mud as microbe source through proportionally mixing, adding soybean oil, high-speed stirring to become small drops, heating to 52 deg.C, reacting, removing liquid, and washing with water or buffering liquid. Its advantage is high effect on suppressing harmful bacteria, reproducting useful bacteria, regulating plant growth, improving soil, and increasing the resistance of plant to diseases.

Description

Biodegradable water-retaining agent and microorganism composite preparation process thereof
Affiliated field: the present invention relates to a kind of biodegradable water-retaining agent and microorganism composite preparation process thereof.
Background technology: super strength water absorbent is shorter in the development time of China, the water-retaining agent of now being produced is except that the effect that water-absorbing-retaining is arranged, what have combines with chemical fertilizer and humic acid, and its effect is the economic benefits and social benefits of water-retaining agent and chemical fertilizer also, fails to solve the problem of pollution by chemical fertilizer in the production.And bio-fertilizer also is the appearance along with green product, and at the new fertilizer that agriculture production is developed, though it can change the biological activity that edatope is recovered soil, if there is not this prerequisite of water, bio-fertilizer can not be given full play to its effect.Now each scientific research institutions' development product mainly is single water-retaining agent product, only has the effect of water-absorbing-retaining, and also having at present its weak point with regard to application is exactly that it easily hardens after drying and is unfavorable for the maintenance of water and soil.And the microorganism fertilizer of exploitation also must be equipped with a large amount of water in use to guarantee the survival of microorganism, if there has not been water microorganism also can not bring into play the effect of its uniqueness, preservation of microorganism simultaneously and transportation also are the problems of a very bad solution.
Summary of the invention: the purpose of this invention is to provide a kind of advantage, recovery biological activity of soil, deteriorating pesticide residue and heavy metal contaminants, the biodegradable water-retaining agent that improves the quality of products and microorganism composite preparation process thereof that keeps beneficial organism bacterium in the soil.The present invention is: a kind of biodegradable water-retaining agent, and it comprises following component:
Starch: 8-15g
Vinylformic acid: C 3H 4O 240-60g
Ammoniacal liquor or alkali (KOH concentration 18-25%) 90-150ml
Catalyzer Potassium Persulphate K 2S 2O 20.1-0.3g
Linking agent glycerol C 3H 8O 32-5g
Microorganism bacterium mud (compound bacilluss such as bacillus, the Arthrobacter) 8-12g that wets, every g living bacteria count 〉=200,000,000.
Microorganism composite preparation process of the present invention is: adopt water-absorbing resin gel embedding method: the sewage of getting domestic sewage factory is inoculated in the enrichment medium by 1% inoculum size, at rotating speed is to cultivate 30h in 133r/min, 30 ℃ the constant temperature shaking table, with enrichment bacterium liquid centrifugal 20min under process 4000r/min, remove supernatant liquor, it is standby to form bacterium mud;
Get vinylformic acid, being neutralized to pH value with ammoniacal liquor or other alkali lye is 7.0, be cooled to 35 degree, add W-Gum, catalyzer, linking agent, tensio-active agent, and get the wet bacterium mud that said process obtains and mix, add soya-bean oil in 1: 3 ratio of monomer and oil, high-speed stirring is dispersed into droplet, is warming up to 52 degree to its reaction and finishes;
The liquid that inclines, water or damping fluid thorough washing can obtain pearl type immobilized cell.
Because water-retaining agent only has the simple function of water-absorbing-retaining, if do not have water not know where to begin though bio-fertilizer can be regulated edatope yet, in order to make a kind of product have the function that these two kinds of modern agriculture are produced product innovation simultaneously, the present invention has developed the biodegradation type water-retaining agent with the microorganism Application of composite, it has the double effects of water-retaining agent and bio-fertilizer simultaneously, by microorganism immobilization embedded technology the two is well combined, thereby with microbial immobilized product, has the bioenvironmental useful dominant strain in the not available adjustment edaphophyte of water-retaining agent root district, make the present invention have the double effects of water-retaining agent and microorganism simultaneously, under the condition of ground moistening, adjust the effect that edatope reaches the comprehensive regulation.The present invention has also solved the price problem of water-retaining agent and microorganism fertilizer, does not have big increase production cost under the prerequisite of double effects having.Reduce the input in the agriculture production by contrast, reduce the burden in the agriculture production.After the present invention concentrates and is applied to farm crop root district, contained beneficial microorganism in the product, duplicate breeding rapidly, they are by seizing nutritive substance, the secretion of the competition of oxygen and bacteriostatic activity material to the ecological position of root face and rhizosphere, form a kind of biological barrier at crop rhizosphere, stop harmful bacterium decide grow, invade, thereby the minimizing soil-borne disease has strengthened the resistance against diseases of crop; Simultaneously in these probiotics reproductive processes, produce various plants growth regulatory substance (Plant hormones regulators,gibberellins, SOD enzyme etc.), promote root system development, make plant growth vigorous, comprehensive nutrition resistance (drought resisting, resistant to lodging) strengthens, and breeds in a large number owing to beneficial microorganism in addition, can increase soil activation, the conversion of organism decomposition and effective nutritive element improves the rhizosphere nutrition environment in the acceleration soil, has improved the effective rate of utilization of the level of supply and the fertilizer of soil nutrient.Also can introduce the bacterial strain of degradable agriculture chemical, to reduce the medicine chemical fertilizer to environment damage.
Microorganism composite preparation process of the present invention adopts the anti-phase suspension synthesis method, and the synthesizing super-strong water-absorbing resin also is embedded in biomass in the water-absorbing resin gel.Be suspension agent with soya-bean oil or whiteruss in the building-up process, water miscible monomer and biological bacteria are water drop (the reaction back forms particle).Synthon is water miscible or hydrophilic material, and dispersion medium is the oiliness solute, and the system viscosity is low, and heat of polymerization is easily got rid of, and is unlikely because of polymerization exotherm, and temperature is too high and the biological bacteria surviving rate is descended; The operation control ratio is more convenient; Molecular weight product is higher, and is more stable, and quality is evenly pure.The principal feature of this method be with vinylformic acid with in the alkali and after, add in the reactor, this just makes reactive system carry out polymerization at neutral or weakly alkaline state, so equipment is difficult for being corroded again, in the alkali and vinylformic acid be in liquid phase, to carry out, regulate desired pH value easily; One step finished.The particle dia of product is 0.01-5mm, generally about 0.05-2mm, and the particle dia size is decided by dispersion agent character and consumption thereof, stirring state.
Embodiment:
The present invention is a kind of biodegradable water-retaining agent, and it comprises following component:
Starch: 8-15g
Vinylformic acid: C 3H 4O 240-60g
Ammoniacal liquor or alkali (KOH concentration 18-25%) 90-150ml
Catalyzer Potassium Persulphate K 2S 2O 20.1-0.3g
Linking agent glycerol C 3H 8O 32-5g
Microorganism bacterium mud (compound bacilluss such as bacillus, the Arthrobacter) 8-12g that wets, every g living bacteria count 〉=200,000,000.
In the present embodiment:
Starch: 12g
Vinylformic acid: C 3H 4O 260g
Ammoniacal liquor or alkali (KOH concentration 18-25%) 110ml
Catalyzer Potassium Persulphate (K 2S 2O 2) 0.2g
Linking agent glycerol C 3H 8O 30.3g
Microorganism bacterium mud (compound bacilluss such as bacillus, the Arthrobacter) g that wets, every g living bacteria count 〉=200,000,000.
Microorganism composite preparation process of the present invention is:
One, the separation and Culture of microorganism:, select separation source.Be generally contaminated soil, as the refuse tip.
1, broken, dispersion treatment.Notice that physical strength can not be excessive, in order to avoid destroy bacterium cell.
2, the making of substratum.Select substratum, select to be fit to the basic medium of growth and breedings such as bacillus, Arthrobacter, determine culture condition.
3, the isolation and purification of target microorganism.Select tangible lawn of morphological specificity or bacterium colony.
4, do microscopical identification or biochemical discriminating cultivation according to the microorganism characteristics.Being accredited as target microorganism, then to do next step be enrichment culture.
5, enrichment culture.Select to be fit to the selection substratum of target microorganism growth and breeding, determine culture condition.
6, will be enriched in microbial bacteria in the nutrient solution through high speed centrifugation, and form bacterium mud precipitation, it is standby that the nutrient solution that inclines takes out bacterium mud.
7, culture presevation.Utilize sand pipe or other proper method preservations, note regular rejuvenation,, prevent bacterial classification variation or decline to guarantee bacterial classification purity.
Two, biology---water-retaining agent composite fertilizer synthesizes
Adopt water-absorbing resin gel embedding method: the sewage of getting domestic sewage factory is inoculated in the enrichment medium by 1% inoculum size, at rotating speed is to cultivate 30h in 133r/min, 30 ℃ the constant temperature shaking table, enrichment bacterium liquid through centrifugal 20min under the 4000r/min, is removed supernatant liquor, and it is standby to form bacterium mud;
Get vinylformic acid, being neutralized to pH value with ammoniacal liquor or other alkali lye is 7.0, be cooled to 35 degree, add W-Gum, catalyzer, linking agent, tensio-active agent, and get the wet bacterium mud that said process obtains and mix, add soya-bean oil in 1: 3 ratio of monomer and oil, high-speed stirring is dispersed into droplet, is warming up to 52 degree to its reaction and finishes;
The liquid that inclines, water or damping fluid thorough washing can obtain pearl type immobilized cell.
Three, medicine:
W-Gum, vinylformic acid, ammoniacal liquor or potassium hydroxide, soya-bean oil, Diisopropyl azodicarboxylate, glycerine, aqueous ethanolic solution
Four, plant and instrument: sterilization tank, constant incubator, supercentrifuge, thermometer, high speed agitator, water-bath, analytical balance.
1, the ultimate principle of anti-phase suspension synthesis method:
The inverse suspension polymerization method is to be dispersion medium with oils (oil phase), and water miscible monomer is water drop (the reaction back forms particle), and initiator (or catalyzer) is dissolved in a kind of implementation method that the monomer aqueous phase carries out polyreaction.Make high molecular suspension be dispersed into drop by violent stirring (or thermal agitation) and dispersion agent, be suspended in the oily medium, carry out the chemical reaction of macromolecular compound; The high molecular chemical reaction that perhaps makes high molecular solia particle be suspended in the oil medium to be carried out.Therefore the macromolecular compound (reactant) that this method adopted is hydrophilic or water miscible material, and dispersion medium is the oiliness solute.The point that merits attention is the aftertreatment of this method, and reacted product removes and must remove the low molecular reaction beyond the region of objective existence of participating in reaction, also will remove the solvent of being carried secretly, will reclaim a large amount of dispersion medium simultaneously.
The inverse suspension polymerization method is one of important method of synthetic macromolecule super strength water absorbent, also can be described as the method for its uniqueness.This is to be wetting ability (or water-soluble) material because make the starting monomer that absorbent resin adopted.
The advantage of suspension polymerization is: the system viscosity is low, and heat of polymerization is easily got rid of, the operation control ratio
More convenient; Molecular weight product is higher, and is more stable, and quality is even, pure.The shortcoming of this method is that product has paucidisperse agent residue.
2. the dispersion of drop is with stable
In the system of monomer-oil, stir owing to carry out brute force, under the effect of shearing force,
The monomer liquid layer will be dispersed into drop.Big drop is stressed, becomes small droplets.Owing to capillary effect, drop becomes microspheroidal again.This microballoon also has the trend of the big drop of the formation of flocking together.Under certain stirring intensity and interfacial tension, the drop that varies in size between disperseing and assembling, constitutes certain running balance, reaches certain average fineness at last.Generally when being aggregated to transformation efficiency when being 20%-70%, drop becomes and has very big stickiness.This moment, two drops ran foul of each other, and often bonded together, and were difficult to break up, and the result bonds soon and forms big bulk, and this is the stage of being clamminess (also claiming critical days).When transformation efficiency reaches more than the 60%-70%, drop is transformed into solid particulate, has not just bondd caked danger.Therefore, when carrying out inverse suspension polymerization, obtain satisfactory sphere polymers, also need to add suspension agent (dispersion agent) for polyreaction is left on pass.
3. dispersion agent and dissemination thereof
Dispersion agent generally has two major types.
(1) the water soluble organic polymer material dispersion agent that belongs to this class has the polyvinyl alcohol of partial hydrolysis and derivative thereof, polyacrylate; Methylcellulose gum, etc. semisynthetic derivatived cellulose; Natural high moleculer eompounds such as gelatin, protein, starch, sodiun alginate.Their mechanism of action mainly is to be adsorbed on the drop surface, forms layer protecting film, plays a part the protective colloid particle.Increase the viscosity of medium simultaneously, hindered the bonding of two drops.The aqueous solution of gelatin, polyvinyl alcohol etc. can also make interfacial tension diminish, and drop diminishes, and is therefore more stable.The definite kind and particulate with water-retaining agent of the selection of dispersion agent and consumption thereof requires to decide.Outside the size and shape of particle-removing, the transparency etc. that also should consider resin also adds low quantity of surfactant, sometimes as auxiliary dispersants except above-mentioned main dispersant.For example sodium lauryl sulphate, sodium laurylsulfonate etc.The consumption of main dispersant is about 0.1%, and the consumption of dispersion aids is 0.01%-0 3%.
4. particulate size and form
The granular size of product and form are mainly determined by stirring intensity and size.Stirring intensity is bigger, and the particle of product is thinner; Rotating speed is low excessively, will make the polymerization caking, and reaction can not be carried out.In addition, oil was generally 3: 1 with the ratio of monomer.Oil is caking or particle chap easily at least; Oil particle at most attenuates, narrow diameter distribution.The kind of monomer and initiator (or catalyzer) and consumption, polymerization velocity, other additives etc. all have bigger influence to particulate size and form, but more complicated, still difficulty is summarized as universal law.

Claims (2)

1, a kind of biodegradable water-retaining agent, it is characterized in that: it comprises following component:
Starch: 8-15g
Vinylformic acid: C 3H 4O 240-60g
Ammoniacal liquor or alkali (KOH concentration 18-25%) 90-150ml
Catalyzer Potassium Persulphate K 2S 2O 20.1-0.3g
Linking agent glycerol C 3H 8O 32-5g
Microorganism bacterium mud (compound bacilluss such as bacillus, the Arthrobacter) 8-12g that wets, every g living bacteria count 〉=200,000,000.
2, according to the microorganism composite preparation process of a kind of biodegradable water-retaining agent that claim 1 provided, it is characterized in that:
Adopt water-absorbing resin gel embedding method: the sewage of getting domestic sewage factory is inoculated in the enrichment medium by 1% inoculum size, at rotating speed is to cultivate 30h in 133r/min, 30 ℃ the constant temperature shaking table, with enrichment bacterium liquid through under the 4000r/min from 20min, remove supernatant liquor, it is standby to form bacterium mud;
Get vinylformic acid, being neutralized to pH value with ammoniacal liquor or other alkali lye is 7.0, be cooled to 35 degree, add W-Gum, catalyzer, linking agent, tensio-active agent, and get the wet bacterium mud that said process obtains and mix, add soya-bean oil in 1: 3 ratio of monomer and oil, high-speed stirring is dispersed into droplet, is warming up to 52 degree to its reaction and finishes;
The liquid that inclines, water or damping fluid thorough washing can obtain pearl type immobilized cell.
CNA031109829A 2003-01-29 2003-01-29 Biodegradable water absorprion agent and its microorganism composite preparation method Pending CN1513891A (en)

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CN1513891A true CN1513891A (en) 2004-07-21

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100341908C (en) * 2005-03-18 2007-10-10 中国科学院理化技术研究所 Template copolymerizing synthetic process of semi-intercrossing network reversible pH sensitive aquagel
CN100516097C (en) * 2007-08-17 2009-07-22 广东工业大学 Method for synthesizing completely biological degradable high-absorbent resin by solution polymerization process
CN100532411C (en) * 2007-08-17 2009-08-26 广东工业大学 Method for synthesizing completely biological degradable high-absorbent resin by anti-phase suspension polymerization
CN101857501A (en) * 2010-06-21 2010-10-13 万光存 Microbe fertilizer microbial inoculum with high water absorbing and retaining properties and preparation method thereof
CN102010482A (en) * 2010-11-02 2011-04-13 中国农业科学院农业环境与可持续发展研究所 Method for preparing super-strong water-absorbing water-retaining agent
CN105170630A (en) * 2015-10-27 2015-12-23 华东理工大学 Combined type soil washing and desorption method and device
WO2016112583A1 (en) * 2015-01-16 2016-07-21 汕头市正能量本草植物研究所 Sewage activating ball and preparation method therefor

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100341908C (en) * 2005-03-18 2007-10-10 中国科学院理化技术研究所 Template copolymerizing synthetic process of semi-intercrossing network reversible pH sensitive aquagel
CN100516097C (en) * 2007-08-17 2009-07-22 广东工业大学 Method for synthesizing completely biological degradable high-absorbent resin by solution polymerization process
CN100532411C (en) * 2007-08-17 2009-08-26 广东工业大学 Method for synthesizing completely biological degradable high-absorbent resin by anti-phase suspension polymerization
CN101857501A (en) * 2010-06-21 2010-10-13 万光存 Microbe fertilizer microbial inoculum with high water absorbing and retaining properties and preparation method thereof
CN101857501B (en) * 2010-06-21 2013-02-20 万光存 Microbe fertilizer microbial inoculum with high water absorbing and retaining properties and preparation method thereof
CN102010482A (en) * 2010-11-02 2011-04-13 中国农业科学院农业环境与可持续发展研究所 Method for preparing super-strong water-absorbing water-retaining agent
WO2016112583A1 (en) * 2015-01-16 2016-07-21 汕头市正能量本草植物研究所 Sewage activating ball and preparation method therefor
CN105170630A (en) * 2015-10-27 2015-12-23 华东理工大学 Combined type soil washing and desorption method and device

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